Increasing the Efficiency of Dewaxing in the Deoiling Stage

During selective treatment, the content of high–melting paraffins and naphthenes that crystallize from solution when the temperature is decreased increases significantly in lube oil cuts after removal of resins and asphaltenes and polycyclic hydrocarbons with short side chains. These hydrocarbons, which have a high melting point, are removed during dewaxing to obtain low-pour lube oil cuts.     

Kinetic Study on the Hydrocracking Reaction of Vacuum Residue Using a Lumping Model

Abstract

Based on the experimental hydrocracking of vacuum residue, a kinetic study using a lumping model was carried out to gain insight into the characteristics of catalytic reactions. The lumped species were the saturates, aromatics, resins, and asphaltenes (SARA) constituents in the residue (798 K⁺) fraction and gas, naphtha, kerosene, gas oil, vacuum gas oil, and coke in the products. The pyrite reaction favoring hydrocracking to lighter products was more temperature-dependent than that using a mixture of pyrite and active carbon. The kinetic study showed that the addition of active carbon to pyrite limited the transformation of resins to asphaltenes.     

Characterization of Asphaltenes and Resins Separated from Water-in-Oil Emulsions

Abstract

Knowledge of the properties and behavior of asphaltenes and resins is indispensable for the design of preventive and curative measure for emulsion problems created by the presence of asphaltene, resins, and other organic and inorganic solids. In order to understand the phenomena of water-oil emulsions formed in Kuwaiti oil fields and determine the factors involved in the stabilization of these emulsions, the role of asphaltenes, resins and wax separated from various samples of oil field emulsions formed in Burgan oil field have been evaluated. Physicochemical properties of asphaltenes, resins, wax, and de-asphalted de-resined (DADR) oil samples have been studied via FT-IR, ¹H, and ¹³C NMR, elemental analysis, and differential scanning calorimetry (DSC). These emulsion samples contain different amounts of water ranges from 24 to 35%, asphaltene content ranges from 0.9 to 1.7%, and resin content from 3.7 to 4.6%. IR-FT spectra were performed to identify the various functional groups which have an effect on the stability of water-oil emulsions. The freezing behavior of an emulsion was characterized by differential scanning calorimetry to determine whether the water in the emulsion is free water or emulsified water.     

Changes in the properties of conventional crude oil before and after CO2 flooding

Abstract

In order to enhance oil recovery of a conventional oil reservoir by CO₂ flooding, the changes in the properties of the crude oil before and after CO₂ flooding are systematically investigated by on-site sampling and experimental testing. The results show that, after CO₂ flooding, the light hydrocarbons of the produced crude oil is increased and the heavy hydrocarbons of the produced crude oil is decreased due to the deposition of resins and asphaltenes in the pores of the formation. In addition, the produced fluid (a mixture of oil and water) has a high water separation rate, the oil- water interface has a high tension value, and the crude oil has a high acid value and a low viscosity. The conclusions can provide a certain guidance for high-efficiency development of a conventional oil reservoir by CO₂ flooding.     

DISTILLATION CHARACTERISTICS AND COMPOSITIONAL ANALYSIS OF ARABIAN LIGHT STRAIGHT RUN NAPHTHA

ABSTRACT

Straight run naphtha is a basic constituent of refined petroteum products. It consists mainly of aliphatic hydrocarbons along with small amounts of naphthenic and aromatic hydrocarbons. It has a wide boiling range between 95°F and 410°F. Currently, its main utilization is as gasoline blend, however, naphtha is a potential feedstock for the production of various petrochemicals. Continuous catalytic reforming of naphtha can produce aromatic compounds in amounts up to 70% of the reformat. Nevertheless, the catalytic reforming process is usually associated with various limitations that may be related to the wide-ranging composition of naphtha. In this study straight run naphtha derived from Arabian Light crude oil was fractionated, and the hydrocarbon composition of its different distillation cuts was determined. The results indicate that, straight run naphtha can be split into two main fractions. A light fraction boiling between ambient temperature and 225°F, consists mainly of C₇ ^(?) and a medium heavy fraction boiling between 225°F and 335°F, consists mainly of C₇ ⁽⁺⁾. Detailed distillation characteristics, along with compositional analysis of SRN seems to be useful for diversifying its processing technologies, and upgrading currently applied processing practices to yield various high-value products and petrochemicals feed stocks.     

COKE CHARACTERISTICS IN RELATION TO THE COLLOIDAL. MATTER OF PETROLEUM FOR THERMAL. PROCESSES

Abstract

The purpose of this work is to research the characteristics of the production of coke in thermal and hydrothermal cracking from residual oils and their deasphalted oils Using ethyl acetate, because it allows the elimination of both resins and asphaltenes (colloidal matter) from the parent oil in only one step. This improves the deasphalted oil as coke precursors and basic nitrogen compounds present in the resin fraction are practically eliminated.

A 104 ml batch autoclave reactor with a cooling system was used for the thermal and hydrothermal cracking experiments. This reactor can withstand temperatures of up to 500^°C, pressures of 500 bar and a rocking velocity of 1 Hz. The influence of the temperature was investigated at 400, 425 and 450^°C and at 0, 20, 40, 80,     

Aquathermolysis of heavy oil in reservoir conditions with the use of oil-soluble catalysts: part I – changes in composition of saturated hydrocarbons

Abstract

This paper is devoted to the study of aquathermolysis processes of heavy oil produced by CSS technology on Boca de Jaruco oil field. Various catalysts based on cobalt, nickel, iron and copper were used for intensification of in-situ upgrading processes of heavy oil. The first paper in series is presented results of transformation of crude oil and its saturate fraction after thermal treatment with and without catalysts by SARA analysis, MALDI mass-spectrometry, FTIR-spectroscopy and gas chromatography. It is revealed, that catalysts provide more deep conversion of asphaltenes and resins into lighter hydrocarbons. Particularly, for the given heavy oil, catalysts based on iron and nickel organic salts are more effective to reduce the content of high molecular weight components (asphaltenes). Saturates fraction after thermal treatment in presence of the catalysts is enriched with lighter alkanes in comparison to the crude oil treated without catalysts. Obtained results show that crude oil recovered by catalytic aquathermolysis processes will be better quality than the original oil in the place.     

The Structural Characterization of Saturate,Aromatic, Resin,and Asphaltene Fractions of Batiraman Crude Oil

Abstract

The structural characterization of fractions of Batiraman crude oil, which is the heavy crude oil from a field in the southeastern part of Turkey, was investigated. Batiraman crude oil and its saturate, aromatic, resin, and asphaltene (SARA) fractions were seperated. Treatment of crude oil with n-heptane provided the separation of asphaltene. Maltene was collected by evaporating the n-heptane from the filtrate. Then, maltene was separeted into saturates, aromatics, and resins by SARA technique. Maltene was separated into saturate, aromatic, and resin fractions using column chromatography. SARA fractions were quantified on a weight percent basis. Fractions of Batiraman crude oil were characterized by elemental analysis, proton nuclear magnetic resonance (¹H NMR) analysis, electrospray ionization mass spectrometry (ESI-MS), and Fourier transform infrared (FTIR) spectroscopy techniques.     

Preparative Subfractionation of Petroleum Resins and Asphaltenes. II. Characterization of Size Exclusion Chromatography Isolated Fractions

Abstract

In the first study of this series, resins and asphaltenes from stable and unstable crude oils have been separated by size exclusion chromatography in three molecular mass ranges (MM: high, medium, and low). In the present study, the isolated fractions were further characterized in order to correlate several of their structural properties with crude oil tendency to solid deposition. Elemental analysis (C, H, S, N), infrared spectrophotometry (IR), and proton nuclear magnetic resonance (¹H NMR) were the characterization techniques performed in order to meet the objective. Hydrogen deficiency and aromaticity appear to be the main parameters governing the intrinsic stability for the studied samples. Oxygen compounds were observed to be more abundant within fractions isolated from unstable oils, particularly in resins and in the low MM range fractions both from resins and asphaltenes. However, causes for the presence of these oxygenates remain open to further study. Experimental evidence gathered during this work suggest the possibility of small compounds acting like natural dispersants of the larger components present in complex mixtures like asphaltenes.     

Comparison Study for the Distribution of Organo-Sulfur Containing Compounds of Two Kuwaiti Crude Oil Distillates

Abstract

This paper deals with the comparison, analysis, and characterization of two Kuwaiti crude oil samples received from different origins. (Burgan and Al-Wafra oil fields). Systematic analysis was conducted for API gravity, sulfur content, metal content, and viscosity. The representative samples of the two Kuwaiti crude oils were fractionated into naphtha (IBP–170^○C), kerosene (170–265^○C), medium gas oil (265–355^○C), and heavy gas oil (355–550^○C) using an 80 L capacity autodistillation unit “AUTODEST-800” according to ASTM D2892 and ASTM D5236. Particular attention was paid to study the distribution of various types of sulfur compounds in each of these wide cuts, which was qualitatively and quantitatively estimated by capillary gas chromatography equipped with a sulfur chemiluminescence detector, which is suitable for a wide range of sulfur systems. The fingerprinting obtained from the analysis of GC-SCD showed different families of organo-sulfur compounds in crudes, including mercaptans, sulfides, thiophenes, benzothiophenes, dibenzothiophene, benzonaphtothiophene, and their alkyl derivatives. From the analyses the behavior and distribution of the refractory and unrefractory sulfur compounds in the two Kuwaiti crude oils can now be easily followed.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 5. CHARACTERIZATION OF THE OILS OBTAINED FROM COAL CO-PROCESSING WITH SUGARCANE BAGASSE OIL

Abstract

In the present work, the chemical characterization of the oils obtained from liquefaction of different coals with sugar cane bagasse oil and also from the liquefaction of coal with monoethanolamine are presented. Characterization of the oil samples was done with the add of spectroscopic and chromatographic techniques, including UV-vis, FTIR, NMR, preparative liquid chromatography (PLC) and high resolution gas chromatography (HRGC).     

PHYSICAL AND CHEMICAL CHARACTERIZATIONS OF ASPHALTENES FROM DIFFERENT SOURCES

ABSTRACT

Asphaltenes and resins are two of the several, but important, heavy organics present in petroleum fluids. Asphaltenes are operationally defined as the non-colatile and polar fraction of petroleum that is insoluble in n-alkanes (i.e., n-pentane). Conversely resins are defined as the non-colatile and polar fraction of petroleum that is soluble in n-alkanes (i.e., n-pentane), and aromatic solvents (i.e., toluene), and insoluble in ethyl acetate. A commonly accepted view in the petroleum chemistry is that crude oil asphaltenes form micelles which are stabilized by adsorbed resins kept in solution by aromatics. Two key parameters that control the stability of asphaltene micelles in a crude oil are the ratio of aromatics to saturates and that of resins to asphaltenes. When these ratios decrease, asphaltene micelles will coalesce and form larger aggregates. The precipitation of asphaltene aggregates can cause problems such as reservoir plugging and wettability reversal.     

A Comprehensive Evaluation of High Viscous Crude Oil from Shuguang No. 1 Zone of Liaohe Oil Field

Abstract

The high viscous crude oil from Shuguang No. 1 zone of Liaohe oil field has the characteristics of high density (ρ ₂₀ = 0.9977 g cm^?3), great viscosity (ν ₁₀₀ = 1223.9 mm² s^?1) and high pour point (48°C), which are similar to those of the residue distillation of general crude oils. It contains no gasoline distillation and the diesel oil fraction yield is just 7.19%. It is often used as fuels after emulsification. But this oil is so vicious that it cannot be atomized uniformly and burned fully. In order to make full use of it, this kind of high viscous crude oil has been evaluated comprehensively and the properties of its various distillations are analyzed respectively. The results indicate that this crude oil contains less wax, but more resins and asphaltene, which belongs to low-sulfur naphthene-base crude oils and it is the suitable material to produce high-quality paving asphalt. Based on its characteristics, the optimum processing scheme is put forward and the high-quality paving asphalt is produced by using the distillation higher than 350°C.     

FREE RADICALS FORMED IN HYDROTREATED COAL LIQUID AND INFLUENCE OF OXYGEN

ABSTRACT

The behavior of radicals formed in hydrotreated coal liquid with heat treatment and the influence of oxygen have been investigated by electron spin resonance (e.s.r.) spectroscopy. A set of e.s.r. spectral lines identified as phenalenyl radical appears from 50^°C as the oil is heated in argon atmosphere. The radical concentration is enhanced with temperature, reaches a maximum between 130 and 150^°C and then decreases at higher temperatures. The radical is very stable even at 200^°C for the sample hydrotreated under mild condition, whereas the radical in the sample treated under severe conditions disappears drastically from 150^°C. When oxygen is introduced in the oil, the radical is converted into semiquinone and/or aryloxy radicals and stable molecules. The treatment in the presence of oxygen at higher temperatures is considered to accompany the formation of other aryloxy radicals by the reaction of aromatic hydrocarbons and oxygen.     

VISCOSITY OF WATER IN OIL EMULSIONS

ABSTRACT

Increase in water cut in oil fields generally calls for an increase in the capacity of transport pipelines. Proper design and operation of the latter requires good knowledge of the thermophysical properties of flow resistance of crude-oil water mixtures. An experimental program aimed at measurements of oil-water emulsion viscosity for water cuts prior to the inversion point was conducted.

The present work reports on measurements of Nimr crude oil-water mixtures viscosity for different water cuts and a typical range of temperatures representative of field conditions (20°-50°C). Three mixing intensities of 10⁶, 5×10⁶ and 15×10⁶ erg/cm-sec generated by a dynamic coalescer and directly relevant to field conditions were used.

The results suggest that the inversion point occurs around a value of water cut of 35%. Both Newtonian and non-Newtonian (pseudo-plastic) behaviour were observed, and the ASTM viscosity model is found to be applicable to the emulsions. The effect of the mixing intensity on the resulting emulsion viscosity was found to be important at low temperatures and decreased at high temperatures. The experimental data fitted the available correlations in the literature.     

Heavy Oil Hydroconversion in the Presence of Ultrafine Catalyst

The hydroconversion of heavy oil in the presence of an in situ synthesized catalyst (MoS₂) is studied. It is shown that ultrafine aggregates of amorphous components and crystalline particles of molybdenum sulfide with a particle diameter of 20–70 nm are formed from catalyst precursor (ammonium paramolydbate) emulsion under hydroconversion conditions in a medium of heavy oil. The kinetic characteristics of the hydroconversion of heavy oil and separate groups of its components—paraffin-naphthene hydrocarbons, aromatic hydrocarbons, resins, and asphaltenes—are determined.     

KINETICS OF HYDROCARBON GAS GENERATION FROM MARINE KEROGEN AND OIL: IMPLICATIONS FOR THE ORIGIN OF NATURAL GASES IN THE HETIANHE GASFIELD, TARIM BASIN, NW CHINA

In this paper we derive kinetic parameters for the generation of gaseous hydrocarbons (C_1‐5) and methane (C₁) from closed‐system laboratory pyrolysis of selected samples of marine kerogen and oil from the SW Tarim Basin. The activation energy distributions for the generation of both C_1‐5 (Ea = 59‐72kcal, A = 1.0×10¹⁴ s^?1) and C₁ (Ea = 61‐78kcal, A = 6.06×10¹⁴ s^?1) hydrocarbons from the marine oil are narrower than those for the generation of these hydrocarbons from marine kerogen (Ea = 50‐74kcal, A = 1.0×10¹⁴ s^?1 for C_1‐5; and Ea = 48‐72kcal, A=3.9×10¹³ s^?1 for C₁, respectively). Using these kinetic parameters, both the yields and timings of C_1‐5 and C₁ hydrocarbons generated from Cambrian source rocks and from in‐reservoir cracking of oil in Ordovician strata were predicted for selected wells along a north‐south profile in the SW of the basin. Thermodynamic conditions for the cracking of oil and kerogen were modelled within the context of the geological framework. It is suggested that marine kerogen began to crack at temperatures of around 120°C (or 0.8 %Ro) and entered the gas window at 138°C (or 1.05 %Ro); whereas the marine oil began to crack at about 140 °C (or 1.1 %Ro) and entered the gas window at 158 °C (or 1.6%Ro). The main geological controls identified for gas accumulations in the Bachu Arch (Southwest Depression, SW Tarim Basin) include the remaining gas potential following Caledonian uplift; oil trapping and preservation in basal Ordovician strata; the extent of breaching of Ordovician reservoirs; and whether reservoir burial depths are sufficiently deep for oil cracking to have occurred. In the Maigaiti Slope and Southwest Depression, the timing of gas generation was later than that in the Bachu Arch, with much higher yields and generation rates, and hence better prospects for gas exploration. It appears from the gas generation kinetics that the primary source for the gases in the Hetianhe gasfield was the Southwest Depression.     

SELECTIVE ISOLATION AND CHARACTERIZATION OF “MINA DO LEÃO” COAL TAR BASES

ABSTRACT

Selective isolation of coal tar bases was performed by using two different separation methods: liquid-liquid extraction (LLE) and column liquid chromatography (CLC). Two cuts, A (boiling range 100°C – 230°C) and B (boiling range 230°C – 300°C), obtained by distillation of “Mina do Leao” coal tar oil, are compared after the isolation of bases by both methods through elemental analysis, infra-red spectroscopy and mass yield. In addition, cut A and its bases generated by both LLE and CLC were investigated by GC/MS. Pyridines, quinolines and anilines are the major classes found in the base fractions obtained by both methods. Although both showed to be equally selective for base isolation, the column liquid chromatography method demonstrated better recovery.     

ASPHALTENIC CRUDE OIL CHARACTERIZATION: AN EXPERIMENTAL INVESTIGATION OF THE EFFECT OF RESINS ON THE STABILITY OF ASPHALTENES

ABSTRACT

High performance liquid chromatography (HPLC) and Thin Layer Chromatographic (TLC) latroscan were used to characterize an asphaltenic stock tank oil (STO) from the North Sea. The whole STO was separated into saturates, aromatics, polars 1 (resins 1), polars 2 (resins 2) and asphaltene fractions. The separated resins (1) and the more polar resins (2), also termed asphaltene peptizing agents, were further characterized by HPLC in terms of their neutral, basic, pyrrolic and acidic components. Resins (1) and resins (2) were mixed in different proportions with whole (original) STO; the resulting mixtures were tested for asphaltene onsets of precipitation due to n-C5 injection at 25° C and 690 kPa. Results of these tests are presented and the observed trends are explained in terms of resins characters and/ or major constituents.     

Rapid group analysis of straight-run petroleum cuts by liquid-adsorption chromatography (LAC) with automatic recording

Summary A method of quantitative group analysis has been developed for bicyclic aromatic hydrocarbons with a minimum content of these hydrocarbons (down to 0.2%) in kerosine and kerosine-gas oil distillates, and also for the analysis of monocyclic aromatic hydrocarbons in naphtha cuts, by a recording method of column liquid-adsorption chromatography (LAC) on-Al₂O₃ in a stream of n-hexane or petroleum ether. The analysis requires 20–25 min, and the chromatographic column can be used repeatedly.Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 4, pp. 51–53, April, 1974.